The present invention relates to carboalkoxy alkyl norbornanes derivatives having the generic formula: ##STR3## wherein each of the lines ++++ and the wavy line represent single or carbon-carbon double bonds; wherein each of R.sub.2, R.sub.3 and R.sub.4 represents hydrogen or methyl and R.sub.1 ' represents hydrogen, methyl or methylene; wherein R.sub.5 represents C.sub.1 -C.sub.4 alkyl; with the proviso that when R.sub.2 is CH.sub.3, R.sub.1 ' is hydrogen and ++++ represents a single bond and the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond; and with the further proviso that when R.sub.2 is hydrogen, R.sub.1 ' is methyl and ++++ represents a carbon-carbon single bond and the wavy line represents a carbon-carbon double bond or a carbon-carbon single bond or R.sub.1 ' is methylene (CH.sub.2) and ++++ is a carbon-carbon double bond and the wavy line is a carbon-carbon single bond produced by the novel process of our invention, and to novel compositions using one or more of such norbornane derivatives to alter, modify or augment or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials.
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply, and to provide more uniform properties in the finished product.
Fruity, jasmine-like, burnt fruit-like, raspberry, sweet, green, seedy, berry-like, red berry-like, blueberry-like, spicy, black pepper-like, herbaceous, clove-like, vermouth-like, strawberry-like and balsamic aromas with fruity, jasmine-like, burnt fruit-like, raspberry, seedy, sweet, berry-like, red berry-like, blueberry-like, spicy, black pepper-like, green, herbaceous, clove-like, vermouth-like, strawberry-like, balsamic and bitter tastes are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors.
Spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity, berry-like, juicyfruit, woody, piney, blueberry, banana, green, herbaceous, strawberry-like and dill aroma and taste characteristics both prior to and on smoking in the mainstream and in the side stream.
Intense, long lasting and pleasant fruity, banana-like, creamy, camphoraceous, herbaceous, sweet, spicy, woody, eucalyptol-like, rum/butterscotch-like, balsamic, green, minty, borneol-like and "medicinal" aromas with strong, chamomile-like, camphor, minty and calamnus-like undertones are desirable in several types of perfume compositions, perfumed articles and colognes.
Arctander, "Perfume and Flavor Chemicals" 1969, Volume I discloses the use in perfume compositions and in foodstuff flavors of camphene carbinyl acetate thus:
"1029: 2,2-Dimethyl-Delta-2-beta-norbornane-2-ethylacetate PA1 "Camphene carbinyl acetate". ##STR4## Mild and sweet-woody odor with a floral-piney undertone. The commercial products are probably not well defined single chemicals, and great variations in odor have been observed. PA1 This ester has been developed in line with the research on Sandalwood type odors. The parent alcohol "Camphene carbinol" was once considered useful as a Sandalwood type material, but is has found more use as a sweetening and enriching ingredient in sophisticated pine fragrances. The title ester finds limited use in perfume compositions of woody character, Fougeres, Pine fragrances, etc. and it blends very well with the Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks, etc."
Meller and Webb, J. Chem. Soc. Perkin Trans II, 1974 (I) 26-31 discloses production of the compounds having the structures: ##STR5## together with several other methyl substituted isomers thereof in admixture, according to the reaction: ##STR6## The Mellor and Webb article however, does not disclose the reaction to take place at low temperatures in the pressence of an alkyl aluminum halide or dialkyl aluminum halide whereby but two isomers are produced in a controlled fashion in high yields thus yielding an organoleptically acceptable mixture of carboalkoxy norbornane derivatives.
Thus, nothing in the prior art indicates production for organoleptic uses of compounds having the generic structure: ##STR7## wherein each of the lines ++++ and the wavy line represent single or carbon-carbon double bonds; wherein each of R.sub.2, R.sub.3 and R.sub.4 represents hydrogen or methyl and R.sub.1 ' represents hydrogen, methyl or methylene; wherein R.sub.5 represents C.sub.1 -C.sub.4 alkyl; with the proviso that then R.sub.2 is CH.sub.3, R.sub.1 ' is hydrogen and ++++ represents a single bond and the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond; and with the further proviso that when R.sub.2 is hydrogen, R.sub.1 ' is methyl and ++++ represents a carbon-carbon single bond and the wavy line represents a carbon-carbon double bond or a carbon-carbon single bond or R.sub.1 ' is methylene (CH.sub.2) and ++++ is a carbon-carbon double bond and the wavy line is a carbon-carbon single bond.
U.S. Pat. No. 4,143,074 discloses, generically, compounds which are esters and contain the norbornyl moiety having the structures: ##STR8## wherein either or both of R.sub.1 or R.sub.2 is hydrogen or lower alkyl, R.sub.3 is hydrogen or lower alkyl and n is zero or 1 and in addition, the compound having the structure: wherein R.sub.6 is alkyl having from one up to eight carbon atoms.